Oleum sulfonation of lignins

ABSTRACT

A sulfonated lignin composition suitable for use as an additive in other chemical compositions and processes having essentially complete water solubility in aqueous medium at all pH levels, and a method of producing such sulfonated water-soluble lignin products by reaction of an unsulfonated or a sulfonated starting lignin compound with oleum, while maintaining the temperature of the reaction below 40° C. for a sufficient time to sulfonate the same. Oleum sulfonation provide an increases the organically bound sulfonic acid content of the starting lignin compound of at least about 4.2 moles sulfonic acid per mole of lignin, while providing essentially complete water solubility of the product at all pH levels.

This application is a divisional of my commonly assigned, co-pendingapplication Ser. No. 07/324,320) now U.S. Pt. No. 5,043,434, which is acontinuation-in-part of my commonly assigned, co-pending U.S. Pat.application Ser. No. 07/298,677 filed Jan. 19, 1989 and entitled"Sulfonation of Lignins". The present invention is directed to theproduction of sulfonated lignin compositions suitable for use asadditives in other chemical compositions and processes, and, moreparticularly, to a lignin sulfonated with oleum to produce a highlysulfonated lignin having essentially complete water solubility at all pHlevels.

BACKGROUND OF THE INVENTION

Lignin is a complex, high-molecular weight polymer occurring naturallyin close association with cellulose in plants and trees. In thepaper-making industry, lignin may be recovered as a by-product of thecellulose product by two principal wood-pulping processes known as asulfite process and a kraft process. In the sulfite process, lignin issolubilized from the cellulosic portion of the wood pulp by directsulfonation, while the kraft process is based on an alkaline degradationmechanism causing cleavage β-aryl ether linkages in the polymeric ligninwhich sequentially result in chemical functions of the phenolic andcarboxylic type. Kraft process lignin generally is isolated by acidprecipitation from the black liquor of the pulping process at a pH belowthe pKa of the phenolic groups.

Depending on conditions under which the lignin is precipitated, theprecipitated lignin may be either in the form of free acid lignin or alignin salt. If lignin is precipitated at a high pH, such as about 9.5to 10, the lignin is obtained in the form of a salt. If this lignin isfurther processed by washing, acidifying to a low pH, such as about 2 to5, and further washed so as to be substantially free of salt andash-forming ingredients, free acid lignin, known as "A" lignin, isobtained. A monovalent salt of lignin, such as an alkali metal salt orammonium salt, is soluble in water, whereas free acid lignin andpolyvalent metal salts of lignin are insoluble in water.

Lignin products are widely employed as additives in various chemicalprocesses and compounds. Because of the high degree of chemical activitycharacteristic of lignin, it has been variously employed as asurfactant, extender, dispersant, reinforcement, absorbent, binder,sequestering agent, emulsifier and emulsion stabilizer, and as astabilizing and protective colloid. Lignin is sold under the trademarkIndulin® by Westvaco Corporation of North Charleston, S.C. Sulfonatedlignin compounds, particularly sodium salts of lignosulfonates, arewidely employed as additives and dispersants in textile dyestuffs andprinting pigments, and such products have been sold for a number ofyears under the trademarks Polyfon® and REAX® by Westvaco Corporation.The degree of sulfonation of lignin generally determines its watersolubility at various pH levels, e. g., sodium salts of sulfonatedlignins are generally water-soluble at alkaline and higher pH levels,while they are water-insoluble at lower or acid pH levels.

Lignosulfonate compounds obtained from the lignin by-product of a kraftpulping process may be produced by treatment of an aqueous solution ofthe same with an aldehyde compound at an alkaline pH to methylolate thelignin, followed by treatment with sodium sulfite or bisulfite at anacid pH to sulfomethylate the methylol group on the phenolic nucleus ofthe lignin molecule. The long side chain of the lignin molecule may alsobe sulfonated by treatment with a sulfite or bisulfite salt.

Napthylene sulfonate compositions suitable for use as additives anddispersants in other chemical compositions, and comparable in some waysto lignosulfonates, have been produced by sulfuric acid sulfonation ofnapthylene. It is known that benzene and other aromatic compounds can besulfonated with concentrated sulfuric acid, but as the concentration ofthe water increases during a reaction, the rate of sulfonationdecreases, the reaction rate being inversely proportional to the squareof the water concentration. Reaction ceases when the acid concentrationreaches a level characteristic of each compound, in the case of benzene,about 78% sulfuric acid.

Much thought has been devoted to methods of carrying out the sulfonationreaction to completion. One approach involves removal of the water asformed, the net result being substantially quantitative utilization ofboth hydrocarbon and acid. It is also understood that certain ligninmaterials heretofore have been treated with sulfuric acid, gaseoussulfur trioxide, and/or oleum at varying concentrations to sulfonate thesame, but such treatments have not indicated that the sulfonated ligninproducts are sufficiently water-soluble to be useful commercially asadditives in preparation of other products and chemical compositions.

In my co-pending, commonly assigned aforementioned parent patentapplication, sulfuric acid sulfonation of lignin has been employed toproduce highly sulfonated lignin products suitable for use asdispersants and additives wherein the sulfonated lignins are soluble atmost pH levels without appreciable precipitation.

BRIEF OBJECTS OF THE INVENTION

It is an object of the present invention to provide an improved methodfor producing a sulfonated lignin product for use as an additive inother chemical compositions and processes and having essentiallycomplete water solubility at all pH levels with a high degree ofsulfonation.

It is another object to provide an improved method of producingwater-soluble sulfonated lignin products by direct oleum sulfonation oflignins.

It is a further object to provide an improved method of increasing thedegree of sulfonation of lignins by reaction with oleum to produce awater-soluble sulfonated lignin product.

It is a further object to produce improved oleum sulfonated ligninproducts suitable for use as additives in other chemical processes andcompositions.

SUMMARY OF THE INVENTION

The present invention is directed to the production of sulfonated ligninproducts and an improved method of producing the same by reaction oflignin compounds with oleum, i.e., sulfur trioxide in concentratedsulfuric acid, to provide a highly sulfonated lignin having essentiallycomplete water solubility. More particularly, it has been found thatreaction of a lignin compound with oleum, while maintaining thetemperature of the reaction below about 40° C., and preferably belowabout 20° C., provides an essentially completely water-solublelignosulfonate suitable for use commercially as an additive in otherchemical compositions and processes. The lignin subsequently may beneutralized to form an alkali salt by treatment with a compound selectedfrom the group consisting of lithium, sodium, potassium, ammonium, andamine salts.

The described oleum treatment has been found to provide a water-solublesulfonated lignin product which, in the case of a sulfate lignin such askraft lignin, contains at least about 4.2 moles of organically boundsulfonic acid per 1000 grams of lignin. When a starting kraft ligninmaterial has not been previously sulfonated, the lignin aftersulfonation with oleum contains at least about 4.2 moles sulfonic acid.When the starting kraft lignin material has been previouslysulfomethylated, as with formaldehyde and a sulfite or bisulfitecompound, further treatment and reaction with oleum in accordance withthe method of the present invention increases sulfonation in the ligninproduct which has been found to produce an organically bound sulfonicacid content of up to as much as about 4.7 moles per 1000 grams oflignin. Both such sulfonated lignin products exhibit essentiallycomplete water solubility at all pH levels.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Lignin materials, which have been previously sulfomethylated,sulfonated, or are unsulfonated, may be effectively sulfonated bytreatment with oleum, i.e., sulfur trioxide in concentrated sulfuricacid, by reaction therewith while maintaining the temperature of thereaction below about 40° C., and preferably below 20° C., for asufficient period of time to obtain a sulfonated lignin product which isessentially completely water soluble at all pH levels.

The degree of solubility of such lignin compounds in aqueous medium maybe measured by comparing their acid precipitation numbers, or values. Asexpressed herein, the acid precipitation number of a lignin compound isthe number of grams of a 50% concentration of H₂ SO₄ needed to startprecipitation of a 37 milliliter solution of 0.5 weight percent lignin.

The method of the present invention may be illustrated by the followinglaboratory examples:

EXAMPLE 1

20 grams of a predried Indulin A lignin (unsulfonated) is dissolved fortwo hours at 110 in 80 grams of oleum (H₂ SO₄ +30% SO₃). The temperatureof the reaction is maintained below 40° C., and preferably at or below20° C., by outside cooling or by controlled lignin addition. After tenminutes, the oleum/lignosulfonate composition is poured into 500 gramsof a mixture of ice and water so that the temperature does not exceed40° C. To remove excess sulfuric acid, if desired, the completelydissolved solution thereof is diluted with about three times its volumeof water and neutralized with lime. The neutralized slurry is filteredto remove calcium sulfate precipitate which forms from the interactionof the lime and sulfuric acid unconsumed in the sulfonation reaction,and to the filtrate is added the requisite amount of sodium carbonatequantitatively to convert the calcium salt of the desired sulfonic acidinto its sodium salt. The resultant calcium carbonate precipitate maythen be removed by filtration and the filtrate which contains thedesired lignin salt evaporated to dryness according to any well-knowndrying procedure to provide the recovered sulfonated sodium salt oflignin which is essentially completely soluble in aqueous medium at allpH levels.

A number of lignin starting materials were sulfonated by oleumsulfonation in accordance with the present invention, and were comparedto sulfuric acid sulfonation of lignins, as in my aforesaid co-pendingapplication, and to prior art products not sulfonated with eithersulfuric acid or oleum. The samples were treated to determine their acidprecipitation numbers (solubility) and sulfonic acid content. The ligninsamples with their acid precipitation numbers and sulfonic acid contentsare set forth in the following table:

                                      TABLE 1                                     __________________________________________________________________________    SULFONIC ACID INCREASE OF VARIOUS LIGNINS                                     AFTER OLEUM TREATMENT                                                                            Acid Precipitation                                                                        Sulfonic Acid                                  Sample             Number      Content (Moles/                                Number                                                                             Lignin        (Grams of 50% H.sub.2 SO.sub.4)                                                           1000 g Lignin)                                 __________________________________________________________________________    1    INDULIN        0.2        0.0                                                 (unsulfonated)                                                           2    INDULIN       10.5        1.7                                                 (8% moisture) sulfonated                                                      with H.sub.2 SO.sub.4                                                    3    INDULIN       12.5         1.85                                               (2% moisture) sulfonated                                                      with H.sub.2 SO.sub.4                                                    4    INDULIN       did not precipitate                                                                       4.35/4.40                                           (8% moisture) sulfonated                                                      with Oleum                                                               5    REAX 83        9.2        1.6                                                 (sulfomethylated)                                                        6    REAX 83       did not precipitate                                                                       4.35/4.40                                           (sulfomethylated)                                                             sulfonated with Oleum                                                    7    POLYFON O      3.4        1.1                                                 sulfonated with                                                               Na.sub.2 SO.sub.3                                                        8    POLYFON O     did not precipitate                                                                       4.25/4.40                                           (sulfonated with Na.sub.2 SO.sub.3)                                           sulfonated with Oleum                                                    9    REAX 88       15.0        2.4                                                 (sulfonated-sulfomethylated)                                             10   REAX 88       did not precipitate                                                                       4.5                                                 (sulfonated-sulfomethylated)                                                  sulfonated with Oleum                                                    11   REAX 100M     65          3.1                                                 (sulfonated-sulfomethylated)                                             12   REAX 100M     did not precipitate                                                                        4.72                                               (sulfonated-sulfomethylated)                                                  sulfonated with Oleum                                                    13   VANISPERSE CB  1.7        0.7                                                 (partially desulfonated                                                       sulfite lignin)                                                          14   VANISPERSE CB 95.5        3.3                                                 (partially sulfonated                                                         sulfite lignin)                                                               sulfonated with Oleum                                                    15   LIGNOSOL NSX 110                                                                            10.9         1.83                                               (sulfite lignin)                                                         16   LIGNOSOL NSX 110                                                                            did not precipitate                                                                        4.1/4.14                                           (sulfite lignin)                                                              sulfonated with Oleum                                                    __________________________________________________________________________

As indicated in Table 1, Samples 1-4 utilized as the starting materialan Indulin® lignin, which is an unsulfonated product. Samples 5 and 6utilized as the starting material REAX 83, which is a ligninsulfomethylated with formaldehyde and a sulfite compound. Samples 7 and8 utilized as the starting material Polyfon 0, which is a sulfonatedlignin produced by Westvaco, and sulfonated by treatment with sodiumsulfite. Samples 9 and 10 utilized as the starting material REAX 88,which is a sulfonated and sulfomethylated lignin obtained bymethylolation and sulfonation with a sulfite or bisulfite compound.Samples 11 and 12 utilized as the starting material a REAX 100 M ligninproduced by Westvaco, which is sulfonated and sulfomethylated bymethylation and sulfonation with a sulfite or bisulfite compound.Samples 13 and 14 are Vanisperse lignins obtained as a partiallydesulfonated sulfite lignin by-product of a sulfite wood-pulpingprocess. Lignosol NSX 110 also is a sulfite lignin produced by LignosolCorporation.

Samples 4, 6, 8, 10, 12, 14, and 16 of Table 1 represent lignin productswhich are sulfonated by direct oleum sulfonation in accordance with thepresent invention.

The lignin starting materials of Samples 1-12 are sulfate lignins, asproduced as a by-product of a kraft wood-pulping process. Samples 14 and16 illustrate the utility of the method of the present invention withsulfite lignins.

As can be seen, from the acid precipitation numbers presented (the acidprecipitation number of 0.2 of Sample 1 represents a mildly acidicprecipitation pH of approximately 6.5), the sulfate lignin samplessulfonated with oleum did not precipitate. In the case of the Vanisperselignin, the sulfite lignin sulfonated with oleum exhibits an extremelyhigh acid precipitation number, and thus, has excellent water solubilityat both acid and alkaline pH levels. Similarly Sample 16, which is asulfite lignin, has a slightly less sulfonic acid content that theoleum-treated sulfate lignins. Samples 2-4 illustrate the effect ofmoisture on the precipitation number and sulfonic acid content.

That which is claimed is:
 1. A sulfonated lignin product having anorganically bound sulfonic acid content of at least about 4.2 moles per1000 grams lignin and having essentially complete water-solubility atall levels of pH prepared by the steps consisting essentially ofdissolving a dry lignin compound, recovered as a by-product of kraft orsulfite wood pulping processes, in oleum while maintaining thetemperature of the reaction below about 40° C. to sulfonate the lignin.2. The sulfonated lignin of claim 1 wherein the dry lignin compound is asulfomethylated lignin and the organically bound sulfonic acid contentis up to about 4.7.